Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO 2021/249878 PCT/EP2021/064965
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Aqueous Pickling Compositions and their Use
The present invention relates to an aqueous, neutral pickling composition for
removal
of rust and scale in a method for pickling metallic substrates and a
concentrate to
produce such compositions. The present invention further relates to such
method and
the use of the compositions for pickling metallic surfaces. Furthermore, the
invention
relates to a method for coating metallic substrates, particularly to improve
corrosion
protection.
BACKGROUND
The non-removal of oxide layers and other residuals after thermal treatment of
metallic
substrates typically raises problems in subsequent conversion coating steps,
resulting
in a reduced adhesion of subsequent coating layers, particularly coating
layers
obtained by cathodic electro deposition coating, thus reducing corrosion
protection.
Therefore, generally, and particularly in the automotive industry, aqueous
cleaning and
pickling solutions having rather extreme pH values are used prior to
conversion
coating. A problem typically associated with highly acidic pickling solutions
is that after
rinsing the surface there is a tendency of film rust formation. Furthermore,
when using
highly acidic or highly alkaline compositions, stricter requirements for
occupational and
industrial safety and safety in transportation must be observed. Moreover,
such
pickling compositions are more aggressive towards the metallic substrates to
be
pickled and the equipment.
To overcome such problems, in recent years an increasing number of fluidic,
neutral
rust and scale removing compositions suitable for iron-based and non-iron
metals and
alloys, and being applicable in dip methods, flooding methods and spraying
methods
have been developed. They are suitable to remove oxide layers from metallic
surfaces
as they occur after thermal deburring, laser cutting and welding operations.
Such
neutral pickling compositions have many advantages compared to mineral acid
based
pickling compositions or strong alkaline compositions. Contrary to strong
acids and
bases, their handling is much easier and it is often possible to clean and
pickle the
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surfaces in one process step. Therefore, an additional cleaning step can often
be
omitted.
Particularly, neutral compositions based on phosphonic acids such as 1-
hydroxyethane-1,1-diphosphonic acid or amino phosphonic acids are used for the
above purposes, because they are known to be complexing agents even in an
essentially neutral environment. The term "neutral", as used herein, refers to
aqueous
compositions having a pH value at 55 C of about 5 to about 9 and thus
encompasses
slightly acidic as well as slightly alkaline aqueous compositions.
On the other hand, phosphonates are typically not the first choice, when it
comes to
cleaning and pickling metallic surfaces of different metal composition. This
particularly
plays a role, when metallic substrates of different composition are to be
cleaned and
pickled with the same cleaning and pickling composition one after each other
or at the
same time, in case of pickling pre-assembled metallic components of different
metallic
composition, such as particularly steel and galvanized steel. This is because
phosphonate-based cleaning and pickling solutions often lack a balanced
pickling
weight loss for different substrates, and have a significantly different
effectiveness on
the surfaces to be cleaned and pickled, depending on the type of metal or
alloy.
WO 2013/156396 Al relates to the improvement of the cleaning performance of
protease containing detergents or cleaning agents with respect to protease-
sensitive
soiling. These cleaning agents rely on the activity or the proteases. WO
2013/156396
Al discloses that it is known, that protease containing detergents show an
improved
cleaning performance, when negatively charged polymers are contained. However,
in
detergents containing high amounts of surfactants their combination with
negatively
charged polymers becomes problematic. To overcome problems associated
therewith,
specific phosphonates were added The detergent concentrates disclosed in
Example
1 of WO 2013/156396 Al contain a comparably low amount of water compared to
the
pickling compositions of the present invention, while the detergent in its
usage form
contains more than 99.8 wt.-% of water. Neither the pH value of these
compositions is
optimized nor are they made to remove metal oxides from metallic substrates,
since
their object is to clean textiles and not to pickle metallic surfaces.
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Consequently, there is a continuing need for improved aqueous, neutral
compositions
providing an improved, particularly balanced pickling behavior when used on
different
substrates and which do not adversely affect subsequent conversion coating
processes. Particularly, the adhesion of subsequent coating layers such as
electrodeposition coating layers, filler, basecoat and/or clear coat layers
should not be
deteriorated.
SUMMARY
This need was met by providing an aqueous composition having a pH value at 55
C
in the range from 5 to 9, containing at least one amino organophosphonic acid
derivative of formula (I)
RtN-11-NR2
(I)
wherein
residues R independently of each other are CH2-PO(OR")2,
residues R' independently of each other are alkylene residues with 2 to 4
carbon
atoms,
residues R" independently of each other are H, Na, K, Li or NH4; and
n is an integer from 0 to 4;
and at least one copolymer, which is water-soluble or water-dispersible and
selected
from the group consisting of at least partially neutralized poly(meth)acrylic
acids and
polyvinylpyrrolidones;
the content of water being in the range from 80 wt.-% to 99.5 wt.-%, based on
the total
weight of the composition.
In the following such composition is called "composition according to the
invention" or
"pickling composition according to the invention".
The present invention further provides a concentrate containing the
ingredients of the
composition according to the invention in a higher concentration, which allows
the
preparation of the composition according to the invention at the place, where
it is
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needed, by dilution with a diluent comprising water and optionally organic
solvents and,
if necessary, by subsequently adjusting the pH value.
The invention further provides a method for pickling a metallic substrate
comprising at
least one step of contacting a metallic substrate with a composition according
to the
invention.
In the following, this method is called "pickling method according to the
invention".
Yet another object of the present invention is a method for coating a metallic
substrate
comprising at least
(a) the pickling method according to the invention, followed by
(b) a step of coating the thus pickled metallic substrate with a conversion
coating
composition, optionally followed by
(c) a step of applying an electrodeposition coating composition; and
optionally
followed by
(d) one or more steps of applying one or more further coating composition(s).
In the following, this method is called "coating method according to the
invention".
A further object of the present invention is the use of the compositions
according to the
invention for pickling metallic substrates.
In the following, this use is called "use according to the invention".
DETAILED DESCRIPTION
Composition according to the invention
Since the composition according to the present invention is an aqueous
composition,
the main ingredient is water. The content of water, based on the total weight
of the
composition ranges from 80 wt.-% to 99.5 wt.-%, more preferred 85 wt.-% to 99
wt.-%,
even more preferred 90 wt.-% to 98.0 wt.-% and most preferred 95 to 97.5 wt.-
%.
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The composition according to the present invention may also contain minor
amounts
of one or more organic solvents which are preferably miscible with or dissolve
in water.
Preferably their amount is 10 wt.-% or less, more preferred less than 5 wt.-%
and even
more preferred less than 3 wt.-% or less than 1 wt.-%, based on the total
weight of the
composition according to the present invention. Most preferred the only
solvent used
in the composition according to the present invention is water.
The compositions according to the invention are preferably aqueous solutions
or
aqueous dispersions, most preferred aqueous solutions.
Compositions according to the invention generally provide a more balanced
pickling,
when used for pickling different metallic substrates. The extend of pickling
can be
compared between different substrates by the determination of the pickling
weight loss.
The pickling weight loss is the loss of material in g/m2 in the pickling
process. The
amount should neither be too low, indicating an insufficient pickling nor too
high,
indicating a surface treatment being too harsh, thus increasing the risk of
damaging
the surface of the substrate, leading to an uneven surface and thus causing an
inferior
adhesion of subsequent coating layers.
A sufficient pickling weight loss starts preferably at about 0.5 g/m2 and
should
preferably not exceed about 2.5 g/m2, whereby exceptions from this range might
be
acceptable depending on the desired application. A balanced pickling is
typically
obtained, when the difference in pickling weight loss (Apwl), comparing
different
metallic substrates pickled with the same pickling composition, is preferably
not larger
than about 0.6 g/m2, even more preferred not larger than 0.4 g/m2 and most
preferred
not larger than 0.3 or 0.2 g/m2. The pickling weight loss, particularly the
afore-
mentioned values and the (Apwl) are determined as described in the
experimental part
of the application. The pickling weight loss values and Apwl values as
mentioned
above, preferably apply to CRS (cold rolled steel) and HDG (hot dip galvanized
steel)
and the comparison of both. However, the pickling compositions according to
the
invention are also suitable for other substrates.
The Amino organophosphonic acid derivatives of formula (I)
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The composition according to the present invention comprises at least one
amino
organophosphonic acid derivative of formula (I)
RtN¨R1-NR2
n (I)
wherein
residues R independently of each other are CH2-PO(OR")2,
residues R' independently of each other are alkylene residues with 2 to 4
carbon
atoms,
residues R" independently of each other are H, Na, K, Li or NH4; and
n is an integer from 0 to 4.
Preferably the compositions of the present invention comprise at least two
different
amino organophosphonic acid derivatives of formula (I) differing in the value
of n.
It was particularly surprising that organophosphonic acid derivatives of
formula (I)
could be used in the composition according to the invention, which, if used
alone cause
an unacceptable high pickling weight loss, while when used in mixture with at
least one
water-soluble or water-dispersible copolymer as defined above, provide for
more
balanced pickling results.
To provide aqueous compositions according to the present invention having a pH
value
at 55 C being in the range from 5 to 9, it might become necessary to
neutralize at
least some of the acidic hydrogen atoms present in residue CH2-P0(OH)2 of the
free
acids, if free acids are employed, thus forming alkali salts or ammonium salts
of the
amino organophosphonic acids. This is preferably done in situ, i.e. in the
already
aqueous composition by pH adjustment with KOH, NaOH, LiOH and/or NH4OH,
particularly preferred with aqueous solutions of these bases. However, it is
also
possible to prepare the salts in advance and to dissolve the salts in the
aqueous
medium. Most preferred R" are independently selected from H, K and Na.
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In formula (I) it is further preferred that R' is an alkylene with 2 or 3
carbon atoms, most
preferred R' is CH2CH2.
Moreover, n is preferably an integer from 0 to 3, even more preferred n = 0, 1
or 2 and
most preferred 0 or 1.
While all definitions of R, R', R" and n can independently be combined, it is
particularly
preferred that residues R independently of each other are CH2-PO(OR")2,
residues R'
independently of each other are alkylene residues with 2 or 3 carbon atoms,
residues
R" independently of each other are H, Na or K; and n is an integer from 0 to
3.
Most preferred residues R independently of each other are CH2-PO(OR")2,
residues
R' are CH2CH2, residues R" independently of each other are H, Na or K; and n
is 0, 1
or 2 even more preferred n = 0 or 1.
Examples of particularly preferred amino phosphonic acids and salts thereof
are amino
tris(methylene phosphonic acid) (i.e. R = CH2-P0(OH)2, R' = CH2CH2 and n = 0),
ethylenediamine tetra(methylene phosphonic acid) (i.e. R = CH2-P0(OH)2, R' =
CH2CH2 and n = 1) and diethylenetriamine penta(methylene phosphonic acid)
(i.e. R
= CH2-P0(OH)2, R' = CH2CH2 and n = 2) and the Li, K, Na and ammonium salts
thereof. Amongst the salts of these exemplified amino phosphonic acids the
sodium
and/or potassium salts are preferred.
It was generally found that a particularly balanced pickling is observed, when
using at
least two different amino phosphonic acid derivatives of formula (I), and the
different
values for n do not differ by more than 2, preferably by not more than 1.
Thus, if two
different amino phosphonic acid derivatives of formula (I) are used, it is
preferred that
An = 1 or 2, preferably An = 1.
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Water-Soluble or Water-Dispersible Copolymers
The term "copolymer" as used herein refers to polymers composed of at least
two
different monomers, preferably two different monomers or three different
monomers
(terpolymers).
The At least Partially Neutralized Poly(meth)acrylic Acids
The term "poly(meth)acrylic acids" as used herein and as commonly used,
encompasses "polyacrylic acids", polymethacrylic acids" and
"poly(acrylic/methacrylic)
acids".
Preferably, the at least partially neutralized poly(meth)acrylic acids are
(meth)acrylic
acid-maleic acid copolymers. Particularly, the at least partially neutralized
poly(meth)acrylic acid is an at least partially neutralized polymer
polymerized from a
mixture comprising (meth)acrylic acid, maleic acid and/or its anhydride and
optionally
a carboxy-free monoethylenically unsaturated monomer.
Such (meth)acrylic acid-maleic acid copolymers are preferably alternating
copolymers,
if no further carboxy-free monoethylenically unsaturated monomer is
copolymerized,
and preferably possess a molar ratio of acrylic acid to maleic acid being
50:50.
Typically, these copolymers are prepared by free radical polymerization. Since
the
monomers employed in their synthesis carry just one polymerizable group, i.e.
the
monoethylenically unsatured group, the copolymers are linear copolymers.
Preferably the weight average molecular weight Mw of the copolymers,
determined by
gel permeation chromatography (GPC) is in the range from 15,000 to 100,000,
more
preferred 20,000 to 90,000, even more preferred 30,000 to 80,000, such as
50,000 to
70,000 g/mol. GPC can be carried out according to DIN 55672-3:2016-03. Such
products are e.g. commercially available under the trademark Sokalan from
BASF
SE, Ludwigshafen, Germany.
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It is also possible to use copolymers, which only differ from the afore-
mentioned
(meth)acrylic acid-maleic acid copolymers in that preferably 0 to 10 mol-%,
more
preferred 1 to 8 mol-% and most preferred 1 to 5 mol-% of the combined amount
(meth)acrylic acid and maleic acid are replaced by a third monoethylenically
unsaturated monomer selected from monomers, which do not contain carboxyl
groups
such as acrylic acid esters or methacrylic acid esters, but which preferably
contain a
hydrophilic group. The above weight average molecular weight ranges also apply
to
theses copolymers.
The Polyvinylpyrrolidones
Besides the at least partially neutralized poly(meth)acrylic acids, water-
soluble or
water-dispersible polyvinylpyrrolidones can be combined with the amino
organophosphonic acid derivatives of formula (I) to obtain a balanced pickling
effect.
Preferred polyvinylprrolidone copolymers are vinyl acetate-vinyl pyrrolidone
copolymers. Particularly, the polyvinylpyrrolidone is preferably polymerized
from a
mixture of vinyl pyrrolidone and vinyl acetate and optionally a further
monoethylenically
unsaturated monomer.
Such vinyl acetate-vinyl pyrrolidone copolymers are preferably random
copolymers
and preferably possess a molar ratio of vinyl acetate to vinyl pyrrolidone
from 30:70 to
70:30, more preferred 30:70 to 60:40 and even more preferred from 30:70 to
50:50,
such as 40:60.
Typically, these copolymers are prepared by free radical polymerization. Since
the
monomers employed in their synthesis carry just one polymerizable group the
copolymers are linear copolymers.
Preferably the weight average molecular weight Mw of the copolymers,
determined by
gel permeation chromatography (GPC) is in the range from 15,000 to 100,000,
more
preferred 20,000 to 90,000, even more preferred 30,000 to 80,000, such as
50,000 to
70,000 g/mol. GPC can be carried out according to DIN 55672-3:2016-03. The
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polydispersity of the copolymers NI,/Mn is preferably in the range from 3 to
7, more
preferred 4 to 6.
It is also possible to use copolymers, which only differ from the afore-
mentioned vinyl
acetate-vinyl pyrrolidone copolymers in that preferably 0 to 10 mol-%, more
preferred
1 to 8 mol-% and most preferred 1 to 5 mol-% of the combined amount vinyl
acetate
and vinyl pyrrolidone are replaced by a third monoethylenically unsaturated
monomer
selected from vinyl monomers, acrylate monomers and methacrylate monomers. The
above weight average molecular weight ranges also apply to these copolymers.
pH Value
The aqueous compositions according to the present invention have a pH value
(determined at 55 C) in the range from 5 to 9, preferably 5.5 to 8.5, more
preferred
from 6.0 to 8.0 and most preferred from 6.5 to 7.5.
Amounts of Amino Organophosphonic Acid Derivatives and Water-Soluble or Water-
Dispersible Copolymers
The compositions according to the invention need to contain at least one amino
organophosphonic acid derivative of formula (I).
The amount of all amino organophosphonic acid derivatives of formula (I)
preferably
ranges from 0.2 to 5.0 wt.-%, more preferred 0.3 to 3.0 wt.-% and most
preferred 0.4
to 2.8 wt.-% based on the total weight of the composition according to the
invention
and being calculated as free acid (i.e. R = CH2-P0(OH)2).
The amount of all water-soluble or water-dispersible copolymers, calculated as
free
acids in case of the partially neutralized poly(meth)acrylic acids, and as
defined for use
in the composition according to the invention preferably ranges from 0.05 to
2.0 wt.-%,
more preferred 0.10 to 1.0 wt.-% and most preferred 0.15 to 0.5 wt.-% based on
the
total weight of the composition according to the invention.
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All wt.-% ranges used in the context of the total specification do not only
apply to the
broadest definition of the respective ingredient(s), but also to any further
preferred
embodiment of the ingredient(s).
The combined amount of all amino organophosphonic acid derivatives of formula
(I)
contained in the composition according to the invention and of all water-
soluble or
water-dispersible copolymers, calculated as free acids in case of the
partially
neutralized poly(meth)acrylic acids, and as defined for use in the composition
according to the invention preferably ranges from 0.25 to 7.0 wt.-%, more
preferably
0.3 to 3.0 wt.-% and even more preferred 0.4 to 1.5 wt.-% and most preferably
from
0.5 to 1.0 wt.-% based on the total weight of the composition of the invention
and being
calculated as free acids in case of the amino organophosphonic acid
derivatives of
formula (I) and as free acids (COON) in case of the at least partially
neutralized
poly(meth)acrylic acids.
Weight Ratios of Amino Organophosphonic Acid Derivatives to the Water-Soluble
or
Water-Dispersible Copolymers
The weight ratio of the sum of amino organophosphonic acids of formula (I) to
the sum
of water-soluble or water-dispersible copolymers as defined for the
composition
according to the present invention is preferably in the range from 1:1 to
30:1, more
preferred 1:1 to 10:1, even more preferred from 1:1 to 5:1 and most preferred
1:1 to
3:1.
Further ingredients
The compositions of the present invention may also contain further ingredients
such
as additives, such ingredients being necessarily different from the amino
organophosphonic acid derivatives of formula (I) and the water-soluble or
water-
dispersible copolymers as defined for the composition according to the present
invention. The further ingredients also differ from water and organic
solvents.
If present, such additives typically not interfere with the pickling effect
provided by the
compositions of the present invention, but add further properties such as an
enhanced
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shelf-life, e.g. obtained by adding preservatives; or an integrated cleaning
or
degreasing effect e.g. obtained by adding surfactants, preferably non-ionic
surfactants.
Unlike household cleaning compositions, such as detergents, particularly
laundry
detergents, the compositions according to the present invention do not contain
proteases, preferably no enzymes at all, because pickling action clearly
differs from
enzymatic cleavage reaction such as cleavage of protein-based dirt and/or
contaminations.
Preferably, the total amount of further ingredients, which differ from the
amino
organophosphonic acid derivatives of formula (I) and the water-soluble or
water-
dispersible copolymers as defined for the composition according to the present
invention, is less than 50 wt.-%, more preferred less than 40 wt.-%, even more
preferred less than 30 wt.-% or less than 20 wt.-%, such as less than 10 wt.-%
of the
combined amount of ingredients consisting of the further ingredients, the
amino
organophosphonic acid derivatives of formula (I) and the water-soluble or
water-
dispersible copolymers as defined for the composition according to the present
invention.
Preferably, the compositions according to the invention do not contain other
pickling
agents or metal ion chelating agents beside the amino organophosphonic acid
derivatives of formula (I) and the water-soluble or water-dispersible
copolymers as
defined for the composition according to the present invention.
Concentrate According to the Invention
The present invention further relates to a concentrate comprising a liquid
medium
composed of water and/or organic solvents; the amino organophosphonic acid
derivatives of formula (I) and the water-soluble or water-dispersible
copolymers as
defined for the composition according to the present invention; and any
further
ingredients of the composition according to the invention. The sum of the
amount of
amino organophosphonic acid derivatives of formula (I); the water-soluble or
water-
dispersible copolymers as defined for the composition according to the present
invention and the optionally contained further ingredients preferably ranges
from 10
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Wt.-% to 90 wt.-% of the total weight of the concentrate, more preferred 20
wt.-% to 90
wt.-%, even more preferred 30 wt.-% to 90 wt.-% or 40 wt-% to 90 wt.-% and
most
preferred 50 wt.-% to 90 wt.-%, based on the total weight of the concentrate.
The concentrates according to the invention most preferably do not contain
proteases
and are preferably enzyme-free.
The concentrate allows the preparation of the composition according to the
present
invention where it is needed, by diluting with a diluent comprising water and
optionally
organic solvents and, if necessary, followed by subsequently adjusting the pH
value at
55 C in the range from 5 to 9, preferably 5.5 to 8.5, more preferred from 6.0
to 8.0 and
most preferred from 6.5 to 7.5. The concentrate is preferably an aqueous
concentrate.
Preferably, the dilution ratio is from 1:1 (volume of the concentrate : volume
of the
diluent) to 1:50, more preferred 1:2 to 1:10 and most preferred 1:3 to 1:5.
Using such concentrates reduces the need of large storage capacities and
facilitates
transportation to the places of use.
Pickling Method According to the Invention
The pickling method according to the present invention includes at least one
step of
contacting a metallic substrate with a composition according to the present
invention.
Metallic Substrate
The term "metallic substrate" as used herein includes substrates of any shape,
such
as flat metallic substrates like simple panels or coils, but also metallic
substrates with
complex shapes like automotive bodies or parts thereof. The term "metallic" as
used
herein comprises pure metals and metal alloys. Particularly preferred examples
of
metals and alloys are cold-rolled steel, galvanized steel such as hot-dip
galvanized
steel or electrolytically galvanized steel and aluminum and its alloys.
Particularly
preferred substrates are cold-rolled steel and galvanized steel, such as hot-
dip
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galvanized steel. Moreover, the term "substrate" also comprises pre-assembled
metal
parts, the metal parts being of the same metal or alloy or the metal parts
being of at
least two different metals or alloys (multi-metal capability of the method).
Contacting the Metallic Substrate with a Composition according to the
Invention
The step of contacting a metallic substrate with a composition according to
the
invention is preferably a step selected from the steps of
(a) dipping a metallic substrate into a composition according to the
invention,
(b) flooding a metallic substrate with a composition according to the
invention; and
(c) spraying a metallic substrate with a composition according to the
invention.
While contacting the metallic substrate the composition can be agitated, e.g.
by stirring
and the like.
The metallic substrate is preferably contacted with the composition according
to the
invention for period ranging from 1 to 15 min, more preferred a period ranging
from 3
to 12 min and most preferred a period ranging from 5 to 10 min.
The temperature of the composition according to the invention during the step
of
contacting the metallic substrate preferably ranges from 20 to 70 C, more
preferred
30 to 65 C and most preferred 40 to 60 C such as 50 to 60 C.
Taking into account the maintenance of the temperature of the composition
according
to the invention in the above ranges and optimizing the contact area of the
substrate
during contacting, it is most preferred to contact the metallic substrate by
dipping the
metallic substrate into the composition according to the invention.
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Optional further Steps of the Pickling Method According to the Invention
The pickling method according to the invention can comprise one or more steps
prior
to the at least one step of contacting a metallic substrate with a composition
according
to the present invention.
It is to be emphasized that the optional further steps described in the
following are not
necessarily the only optional steps possible in the pickling method according
the
invention. Particularly any further cleaning, rinsing and/or drying step may
be carried
out in addition to the preferred optional steps, if desired.
Particularly, the pickling method may comprise, prior to the at least one step
of
contacting a metallic substrate with a composition according to the present
invention
(iv), at least one cleaning step (i) preferably followed by at least one
rinsing step (ii),
even more preferred followed by two rinsing steps (ii) and (iii).
Therefore, a preferred pickling method according to the present invention
comprises
(i) a step of contacting a metallic substrate with a cleaning composition,
optionally followed by
(ii) a step of rinsing the metallic substrate with a first rinsing
composition,
optionally followed by
(iii) a step of rinsing the metallic substrate with a second rinsing
composition,
followed by
(iv) a step of contacting a metallic substrate with a composition according
to the
present invention.
Step (i) of contacting the metallic substrate with a cleaning composition can
be carried
out in the same manner as the step of contacting the metallic substrate with a
composition according to the present invention except for using the cleaning
composition instead of the composition according to the present invention.
Most
preferred are spray cleaning and/or dip cleaning. The temperature of the
cleaning
composition used in step (i) is preferably in the range from 20 to 70 C, more
preferred
30 to 65 C and most preferred 40 to 60 C such as 45 to 60 C. The duration
of
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contacting the metallic substrate with the cleaning composition preferably
ranges from
0.5 min to 15 min, more preferred 1 min to 10 min, most preferred 3 min to 5
min.
The cleaning composition preferably has an alkaline pH value in the range from
8 to
12, more preferred 9 to 11, such as 10 to 11 and preferably contains at least
one of
caustic, phosphonates, surfactants and complexing agents.
Suitable cleaning agents are for example commercially available from Chemetall
GmbH (Frankfurt, Germany) under the tradename Gardocleane.
The rinsing steps (ii) and (iii) are preferably carried out by spray or dip
applying,
preferably dip applying the respective rinsing compositions. The rinsing
compositions
are typically water or water containing diluted ingredients of the previous
treatment
step due to the unavoidable drag over from the previous bath, if dip
application is
chosen.
The first rinsing composition preferably has a pH value in the range from 9 to
12, due
to drag over from the previous cleaning composition and preferably contains
all
ingredients of the cleaning composition, but water-diluted.
The second rinsing composition preferably has a pH value in the range from 8
to 11,
due to the drag over from the first rinsing compositions and preferably
contains all
ingredients of the first rinsing composition, but water-diluted.
The rinsing steps can also be carried out with water only, particularly in
laboratory-
scale experiments.
The above sequence of steps (i) to (iv) is also a preferred embodiment of step
(a) of
the method for coating according to the invention.
The pickling method according to the invention can also comprise one or more
steps
subsequent to the at least one step of contacting a metallic substrate with a
composition according to the present invention (iv), namely one or more
rinsing steps
(v) to (vii).
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Therefore, a preferred pickling method according to the present invention may
also
corn prise
(iv) a step of contacting a metallic substrate with a composition according
to the
present invention, followed by
(v) a step of rinsing the metallic substrate with a third rinsing
composition,
optionally followed by
(vi) a step of rinsing the metallic substrate with a fourth rinsing
composition, and
optionally followed by
(vii) a step of rinsing the metallic substrate with a fifth rinsing
composition.
The rinsing steps (v), (vi) and (vii) are preferably carried out by spray or
dip applying
the respective rinsing compositions. The rinsing compositions can just be
composed
of water, but are typically the water-diluted compositions from the respective
previous
steps due to the drag over from the respective previous steps. Carrying out
the rinsing
steps (v) to (vii) is particularly preferred if the pickling method according
to the present
invention is carried out continuously. In such case an accumulation of iron
compounds
in the pickling composition occurs if iron containing metallic substrates are
pickled.
Such iron compound can be washed-off in the respective rinsing step(s).
The above sequence of steps (iv) to (vii) is also a preferred embodiment of
step (a) of
the method for coating according to the invention.
To keep such iron compounds in solution, it is preferred that the third
rinsing
composition preferably has an acidic pH value in the range from 1 to 3 and
preferably
further contains the ingredients of the previous pickling composition, but
water-diluted.
To avoid the formation of a rust film after the acidic rinse, the fourth
rinsing composition
preferably has an alkaline pH value in the range from 9 to 12 and preferably
contains
caustic plus a complexing agent. Rust film formation may particularly occur,
if the
pickling method is run as a continuous process and this process is interrupted
and/or
the time between the steps becomes too long.
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If the pickling method according to the present invention is followed
particularly by a
phosphate conversion coating step, it is preferred that the fifth rinsing
composition
preferably has a pH value in the range from 9 to 10 and contains the
ingredients of
the forth rinsing composition, due to drag over, but water-diluted.
Typically, prior to a phosphate conversion coating step an activation step is
carried out
and prior to this conversion coating step it is neither preferred that the pH
value of a
rinsing composition is too high or too low. Therefore, it is particularly
preferred that the
pH value of the fifth rinsing solution is in the afore-mentioned slightly
alkaline or neutral
range. Particularly preferred in step (vii) is rinsing with water.
Of course, all steps prior to the step of contacting a metallic substrate with
a
composition according to the present invention and the steps subsequent to the
step
of contacting a metallic substrate with a composition according to the present
invention
can be carried out in combination in the pickling method according to the
present
invention.
In such case, the pickling method according to the invention preferably
comprises
(i) a step of contacting a metallic substrate with a cleaning composition,
optionally followed by
(ii) a step of rinsing the metallic substrate with a first rinsing
composition,
optionally followed by
(iii) a step of rinsing the metallic substrate with a second rinsing
composition,
followed by
(iv) a step of contacting the metallic substrate with a composition
according to
the present invention, followed by
(v) a step of rinsing the metallic substrate with a third rinsing
composition,
optionally followed by
(vi) a step of rinsing the metallic substrate with a fourth rinsing
composition, and
optionally followed by
(vii) a step of rinsing the metallic substrate with a fifth rinsing
composition.
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The cleaning composition, the rinsing compositions and the composition
according to
the invention being defined as above. The above sequence of steps (i) to (vii)
is also
a preferred embodiment of step (a) of the method for coating according to the
invention.
Coating Method According to the Invention
It is further provided a method for coating a metallic substrate comprising at
least
(a) the pickling method according to the invention, followed by
(b) a step of coating the thus treated metallic substrate with a conversion
coating
composition obtaining a conversion coating layer, optionally followed by
(c) a step of applying an electrodeposition coating composition obtaining an
electrodeposition coating layer; and optionally followed by
(d) one or more steps of applying one or more further coating composition(s)
obtaining one or more further coating layer(s).
It is to be emphasized that the steps of the coating method according to the
invention
as described above are not necessarily the only steps possible in the coating
method
according the invention. Particularly any further rinsing, drying and/or
curing step(s)
may be carried out in addition to the above steps, if desired.
Thus, it is preferred to have at least one rinsing step (b") subsequent to
step (b) and
prior to step (c). It is also preferred to have at least one rinsing step (c')
followed by a
curing step (c") subsequent to step (c).
Preferably, the coating obtained in the coating method according to the
invention is a
multilayer coating. Even more preferred the coating obtained in the coating
method
according to the invention is a coating comprising a conversion coating layer,
an
electrodeposition coating layer and preferably at least one further coating
layer.
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Step (a)
Thus, the coating method according to the invention comprises ¨ as a
pretreatment
step ¨ at least step (a), i.e. the pickling method according to the invention,
particularly
at least step (iv) of the pickling method according to the invention.
More preferably step (a) comprised in the coating method according the
invention
comprises steps (iv), (v), (vi) and (vii) of the pickling method of the
invention.
Even more preferred, step (a) comprised in the coating method of the invention
comprises steps (i) to (vii) of the pickling method according to the
invention.
Step (b)
Generally, any known conversion coating composition can be used in step (b) of
the
method for coating according to the present invention.
The conversion coating compositions used in the present invention are
preferably
acidic conversion coating compositions.
Preferably the conversion coating compositions used in the method for coating
according to the present invention are selected from
phosphate conversion coating compositions, such as Ni-containing and
Ni-free zinc phosphating compositions and trication phosphating
compositions, the phosphate conversion coating compositions
containing zinc ions and at least one of manganese ions and nickel ions,
organosilane based conversion coating compositions containing at least
one organosilane and/or its hydrolysis products and/or its condensation
products; and
passivating conversion coating compositions containing at least one
compound selected from the groups of zirconium compounds, titanium
compounds and hafnium compounds.
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If a phosphate conversion step, particularly a zinc phosphating step or a
trication
phosphating step is carried out as step (b), it is preferred to carry out an
additional
activation step (a') after step (a) and prior to step (b). If carried out, the
activation step
(a') is carried out by contacting the metallic substrate subsequent to step
(a) and prior
to step (b) with an activation composition. Contacting is preferably carried
out by
dipping, flooding or spraying as descripted for contacting a metallic
substrate with the
composition according to the invention. Most preferred is contacting the
metallic
substrate by dip application of the activation composition. The duration of
the
contacting step with the activation composition preferably ranges from 5 to
300
seconds, more preferred 10 to 200 seconds and most preferred 20 to 90 seconds
such
as 30 to 60 seconds. Activation compositions or solutions are for example
available
from Chemetall GmbH (Frankfurt, Germany) under the trademark Gard lane V and
Gardolenee ZL.
If an activation step is carried out, the activation composition used therein
preferably
contains zinc phosphate crystals and/or titanium phosphate crystals, which
facilitate
the deposition of the phosphate conversion layer.
If a phosphate conversion step, particularly a zinc phosphating step or a
trication
phosphating step is carried out as step (b), it is preferred to carry out an
additional
passivation step (b') after step (b) and prior to step (c). Passivation
compositions are
for example available from Chemetall GmbH (Frankfurt, Germany) under the
trademark Gardolene D.
Amongst the zinc phosphating compositions, Ni-containing compositions may be
employed. However, for environmental reasons, Ni-free zinc phosphating
conversion
coating compositions are preferred, which contain Zn ions and Mn ions. A
further
variant of zinc phosphating conversion coating compositions are the so-called
trication
phosphate conversion coating compositions containing Zn, Mn and Ni ions.
Phosphate
conversion coating compositions are for example available from Chemetall GmbH
(Frankfurt, Germany) under the trademark Gardobond .
Organosilane-based conversion coating compositions preferably contain at least
one
organosilane, the term "organosilane" including its hydrolysis products and
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condensation products, and optionally compounds selected from the group of
zirconium compounds, titanium compounds and hafnium compounds. Such
compositions are for example available from Chemetall GmbH (Frankfurt,
Germany)
under the trademark Oxsilan0 to produce thin-film systems.
Passivating conversion coating compositions preferably contain at least one
compound selected from the groups of zirconium compounds, titanium compounds
and hafnium compounds, more preferably a fluoro complex of titanium, zirconium
and/or hafnium. Such conversion coating compositions optionally contain one or
more
organosilanes the term "organosilane" including its hydrolysis products and
condensation products.
Step (c)
In step (c) an electrodeposition coating composition is applied to the
conversion
coating layer formed in step (b). Electrodeposition coating compositions are
aqueous
coating compositions which are applied by dip coating, i.e. dipping the
pickled,
conversion coated metallic substrate into the electrically conductive, aqueous
electrodeposition coating composition and applying a direct voltage between
the
substrate and a counter electrode.
The electrodeposition coating composition is an anodic or cathodic
electrodeposition
coating composition, preferably a cathodic electrodeposition coating
composition.
Cathodic electrodeposition coating compositions are preferably selected from
epoxy-
type and poly(meth)acrylate-type electrodeposition coating compositions. They
are
applied according to the coating manufacturers specifications.
Subsequent to step (c) the formed electrodeposition coating layer is
preferably rinsed
(step (c')) and cured (step (c")) according to the paint manufacturers
specifications.
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Step (d) or Steps (d)
Subsequent to the electrodeposition coating step (c) it is preferred to apply
one or more
further coating compositions. Such further coating compositions are preferably
selected from water-based coating compositions, solvent-borne coating
compositions
or UV-curing coating compositions. However, so-called powder coating
compositions
can also be applied.
Particularly preferred at least one of a filler coating composition, a
basecoat
composition and a clear coat composition is applied. If a plurality of coating
layers is
applied (i.e at least two coating compositions), the application can be
carried out wet-
in-wet and afterwards the coating layers can be cured simultaneously. However,
it is
also possible to carry out drying steps and/or curing steps between the
application of
at least some or all of the plurality of coating compositions as may be used
in step(s)
(d).
The method for coating metallic substrates according to the invention provides
well
adhering, corrosion-resistant coatings, preferably multilayer coatings.
Use according to the Invention
The invention further provides the use of the compositions according to the
invention
for pickling metallic substrates, the metallic substrates being the metallic
substrates as
described above.
The compositions and their use provide for a balanced and mild, but
sufficiently high
pickling, if applied to different metallic substrates, thus allowing to pickle
different
metallic substrates with the same pickling composition one after each other,
or if
desired, in form of pre-assembled parts comprising different metallic
substrates.
In the following the invention will be further explained by providing working
examples.
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EXAMPLES
Testing Procedures
Determination of the Pickling Weight Loss
Two test panels made of CRS (cold-rolled steel) and HDG (hot dip galvanized
steel)
were in each case weighed before treatment with one of the pickling solutions.
After pickling, all panels were rinsed with deionized water, dried and
weighed. The
weight loss caused by the treatment with pickling solution (i.e. the pickling
weight loss)
in each case represents the removal of material. In each case the average of
the three
panels was calculated.
The pickling weight loss should preferably not exceed 2.5 g/m2, because
surface
defects are likely to occur resulting in insufficient adhesion of any
subsequent coating
layers. Furthermore, the pickling weight loss should preferably not be below
0.5 g/m2,
because otherwise insufficient pickling is likely.
A balanced pickling weight loss for a specific pickling composition is
achieved, if the
difference in pickling weight loss for CRS and HDG is 0.6 g/m2 or less and the
pickling
weight loss for both materials is in the range from 0.5 g/m2 to 2.5 g/m2.
Determination of the Conversion Coating Layer Weight
The conversion layer weight for the pickled zinc phosphatized metallic
substrates is
determined by XRF analysis and expressed in g/m2, calculated as P205.
In case of the pickled zinc phosphatized metallic substrates, the conversion
layer
weight is supposed to be good, if it does not exceed 4.0 g/m2 for CRS and if
it does
not exceed 3.5 g/m2 for HDG.
The conversion layer weight for the pickled Oxsilane treated metallic
substrates is
determined by XRF analysis and expressed in mg/m2, calculated as Zr.
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In case of the pickled Oxsilane 9832 treated metallic substrates, the
conversion layer
weight is supposed to be good, if it does not exceed 150 g/m2 for CRS and if
it does
not exceed 150 g/m2 for HDG.
Cross-Cut Adhesion Test
The pickled, conversion coated and electrodeposition coated metallic
substrates were
subjected to the cross-cut adhesion test according to DIN EN ISO 2409.
If no delamination is observed, the results are rated "0", complete
delamination is rated
"5". All other grades of delamination are between "0" and "5". An acceptable
delamination is rated "0" or "1". The results are average results from two
panels.
Electrochemical Delamination Test
The pickled, conversion coated and electrodeposition coated metallic
substrates were
subjected to the electrochemical delamination test according to the current AA-
0175
norm from BMW.
Delamination is measured in millimeter [mm]. An acceptable delamination is
less 2
mm. The results are average results from two panels.
Preparation Examples
Pickling of Metallic Substrates
Pickling for the determination of the pickling weight loss
Panels made of CRS (cold-rolled steel) and HDG (hot dip galvanized steel) were
cleaned with an aqueous solution of Gardoclean S5411 (20 g/L; pH value 10.5)
at a
temperature of 55 C for 3 min by spray cleaning and 5 min by dip cleaning.
Afterwards
the panels were rinsed with water containing the ingredients of the drag over
of the
previous composition (cleaner bath).
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Two panels in each case were immersed for 10 minutes in a bath comprising one
of
the inventive pickling compositions 11 and 12; or one of the comparative
pickling
compositions Cl, C2 or C3 (see Table 1). The compositions were aqueous
solutions
of compounds A, B or C (comparative); or aqueous solutions of inventive
mixtures of
compounds A and B (11), and B, C and E (12), as shown in Table 1. The baths
had a
temperature of 55 C. The panels were rotated at a speed of 250 rpm.
Table 1
Pickling Composition Compound(s) Amount [wt.-%] pH valuel
Cl A 0.4 7.5
C2 B 1.3 7.5
C3 C 1.3 7.5
A 0.2
11 7.5
0.5
1.3
12 C 1.3 7.5
0.2
I adjusted by addition of a 50 wt.-% KOH solution in water
A: copolymer based on acrylic acid, maleic acid and a carboxy-free,
hydrophilic
ethylenically unsaturated monomer
B: compound of formula (1) with R = CH2-P0(OH)2, R' = CH2CH2 and n = 0
C: compound of formula (1) with R = CH2-P0(OH)2, R' = CH2CH2 and n = 1
D: vinyl acetate-vinyl pyrrolidone (40:60) copolymer (molar ratio)
After pickling the panels, the panels were taken out of the baths and rinsed
with water
containing some drag over from the previous step. The thus pickled panels were
dried
and used to determine the pickling weight loss according to the above
described
procedure.
Pickling as Pretreatment before carrying out the Coating Steps
Further panels made of CRS and HDG, respectively, were cleaned and rinsed as
described above and subsequently immersed for 5 and 10 minutes, respectively,
in a
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bath comprising one of the pickling compositions as shown in Table 2. The
pickling
compositions are inventive aqueous solutions of mixtures of compounds B and C
(13)
and A and E (14) in the respective amounts. The baths had a temperature of 55
C and
was stirred at a speed of 250 rpm.
Table 2
Pickling Composition Compound(s) Amount [wt.-%] pH
valuel
A 0.2
13 6.8
0.5
A 0.2
14 6.8
0.5
I adjusted by addition of KOH solution in water
A: copolymer based on acrylic acid, maleic acid and a carboxy-free monomer
B: compound of formula (1) with R = CH2-P0(OH)2, R' = CH2CH2 and n = 0
E: compound of formula (1) with R = CH2-P0(OH)2, R' = CH2CH2 and n
= 2
The thus pickled panels were first rinsed with slightly acidic water and
subsequently
rinsed with alkaline water prior to conversion coating the thus pickled
metallic
substrates were used wet before carrying out conversion coating.
Conversion Coating of Pickled Metallic Substrates
The pickled test panels made of CRS and HDG (pickled with the pickling
composition
according to Table 2) were in each case contacted with either a zinc phosphate
based
conversion coating composition (available from Chemetall GmbH, Frankfurt,
Germany)
or a silane based conversion coating compositions (Oxsilan 9832, commercially
available from Chemetall GmbH, Frankfurt, Germany).
Zinc Phosphating Conversion Coating
The panels to be coated with the zinc phosphate conversion coating composition
were
activated with Gardolene V 6559 (commercially available from Chemetall GmbH,
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Frankfurt, Germany) by dipping the panels into a 1 g/L solution of Gardolenee
V 6559
for 30 to 60 s at room temperature (about 23 C).
Zinc phosphating was carried out by dip coating the activated panels into
Gardobonde
24 T (commercially available from Chemetall GmbH, Frankfurt, Germany) for 3
min at
55 C.
Subsequently, the panels coated with the zinc phosphate conversion coating
composition were passivated with Gardolenee D 6800/8 (commercially available
from
Chemetall GmbH, Frankfurt, Germany) by dipping the panels into a 2.1 g/L
solution of
Gardolenee D 6800/8 (pH 4.3) for 30 seconds at room temperature (about 23 C).
Silane-based Conversion Coating
The panels to be coated with the silane-based conversion coating composition
were
neither activated prior to conversion coating, nor passivated after conversion
coating.
To produce the conversion coating layers, the pickled panels were dipped in a
bath
comprising the Oxsilan conversion coating composition (Oxsilane 9832) for 3
min at
a temperature of 32 C.
After conversion coating and prior to electrodeposition coating the conversion
coated,
pickled metallic substrates were rinsed with deionized water.
The thus conversion coated panels were subjected to the determination of the
conversion layer weight as described above.
Electrode position Coating of The Conversion Coated, Pickled Metallic
Substrates
The conversion coated, pickled CRS panels were subjected to electrodeposition
coating with CathoGuard 800 electrodeposition coating composition, which is
commercially available from BASF Coatings GmbH (MOnster-Hiltrup, Germany).
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The thus electrodeposition coated panels were rinsed and dried in the oven at
a
temperature of 175 C for 15 min and ended up with a thickness of 18-22 pm
prior to
cross-cut testing and electrochemical delamination testing as described above.
Test Results
Table 3 below shows the results from the pickling weight loss determination
and
confirms that the inventive mixtures show a mild, but sufficient pickling, all
in the range
of 0.7 g/m2 to 0.9 g/m2 on both, CRS and HDG, and an excellent balance in
pickling
weight loss of just 0.1 g/m2.
To the contrary, using the pickling solutions comprising only the polymer (Cl)
or only
the amino organophosphonic acid derivative of formula (1) (C3), show an
insufficient
pickling, or in case of C2 an aggressive pickling on HDG accompanied by an
unbalanced pickling.
Table 3
Pickling Pickling Weight Loss [g/m2]
Composition CRS HDG A Pickling Weight Loss
[g/m2]
Cl 0.2 0.1 0.1
C2 0.7 7.5 6.8
C3 0.5 0.3 0.2
11 0.7 0.8 0.1
12 0.9 0.8 0.1
The results shown in Table 4 below reflect the weight of the zinc phosphate
conversion
layers in g/m2 calculated as P205 obtained on CRS and HDG panels, pickled for
5 and
min respectively. The target value is preferably 4 g/m2 or below for CRS and
below
3.5 g/m2 for HDG, which is observed in all cases, when pickling is carried out
for 5 min
and 10 min.
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Table 4
Pickling Conversion Layer Weight / Zinc Phosphate Conversion
[g/m2]
Composition CRS (5 min /10 min) HDG (5 min /10 min)
13 3.4 / 4.0 3.2 / 3.0
14 3.0 / 3.7 3.2 / 3.2
The results shown in Table 5 below reflect the weight of the Oxsilan 9832
conversion
layers in g/m2 calculated as Zr obtained on CRS and HDG panels, pickled for 5
and 10
min, respectively. The target value is preferably below 150 g/m2 for CRS and
HDG,
which is observed in all cases, when pickling is carried out for 5 and 10 min.
Table 5
Pickling Conversion Layer Weight / Oxsilan 9832 Conversion
[g/m2]
Composition CRS (5 min / 10 min) HDG (5 min / 10 min)
13 107 / 106 64 / 68
14 100 / 85 60 / 64
Table 6 shows the cross-cut adhesion test results obtained for CRS panels,
pickled for
5 and 10 min, respectively, and conversion coated with Oxsilan 9832 before
applying,
rinsing, drying and curing a CathoGuard 800 cathodic electrodeposition
coating
layer. As all examples show, no adhesion failure is observed for any sample.
Table 6
Cross Cut Adhesion Test Results after
Pickling Electrodeposition Coating with CathoGuard 800
Composition CRS/Oxsilan 9832
(5 min/10 min)
13 0 / 0
14 0 / 0
Table 7 shows the results from the electrochemical delamination test on
CRS/Oxsilan
9832.
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Table 7
Electrochemical Delamination in [mm]
Pickling Composition CRS/Oxsilan 9832
(5 min)
13 <1
14 <1
Thus, Tables 6 and 7 show that the coating layers applied to inventively
pickled metallic
substrates possess a perfect adhesion in the cross-cut adhesion test as well
as the
electrochemical delamination test. A good delamination value is a value < 2.0
mm.
Both samples show very good values below 1 mm.
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